WO2010018707A1 - Corps fritté à base d’oxyde de gallium-oxyde d’étain et film d’oxyde - Google Patents

Corps fritté à base d’oxyde de gallium-oxyde d’étain et film d’oxyde Download PDF

Info

Publication number
WO2010018707A1
WO2010018707A1 PCT/JP2009/060430 JP2009060430W WO2010018707A1 WO 2010018707 A1 WO2010018707 A1 WO 2010018707A1 JP 2009060430 W JP2009060430 W JP 2009060430W WO 2010018707 A1 WO2010018707 A1 WO 2010018707A1
Authority
WO
WIPO (PCT)
Prior art keywords
sintered body
oxide
gallium
phase
thin film
Prior art date
Application number
PCT/JP2009/060430
Other languages
English (en)
Japanese (ja)
Inventor
太 宇都野
一吉 井上
健治 後藤
Original Assignee
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to JP2010524680A priority Critical patent/JPWO2010018707A1/ja
Publication of WO2010018707A1 publication Critical patent/WO2010018707A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6582—Hydrogen containing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/664—Reductive annealing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase

Definitions

  • the present invention relates to a gallium oxide-tin oxide based oxide sintered body, a method for producing the same, and an oxide film.
  • the present invention relates to a tin oxide-based transparent amorphous thin film material such as a display panel or a touch panel.
  • the transparent conductive film has both high visible light transmittance and high conductivity, such as a liquid crystal display element, a transparent electrode of a display element such as a plasma light emitting element, a transparent electrode of a solar cell, a heat ray reflective film of automobile or architectural glass, a CRT Widely used as a transparent heating element for various types of anti-fogging, such as antistatic films or frozen and refrigerated showcases.
  • an ITO (tin-doped indium oxide) film is mainly used because a low resistance film can be easily obtained.
  • ITO films are widely used as display element electrodes.
  • a low-cost zinc oxide-based transparent conductive film and a low-cost, highly chemical-resistant tin oxide-based transparent conductive film are also known.
  • ITO is an obstacle to cost reduction because indium which is the main component is expensive.
  • the chemical resistance with respect to an acid, an alkali, etc. is low. Therefore, it is difficult to apply the zinc oxide-based transparent conductive film to industrial products such as display elements.
  • the tin oxide-based transparent conductive film is extremely excellent in chemical resistance as compared with the ITO film and the zinc oxide-based transparent conductive film.
  • the tin oxide system is produced by a spray method or a CVD method as an industrial production method, but it is difficult to form a uniform film thickness.
  • chlorine, hydrogen chloride, etc. are generated during film formation, and there is a problem of environmental pollution due to these exhaust gases (or effluents), and there is a need to establish a film formation method by sputtering that does not generate chlorine or hydrogen chloride. .
  • a sputtering method which is easy to obtain a uniform thin film and has little environmental pollution is suitable.
  • Patent Document 1 proposes a transparent conductive oxide composed of one or more selected from the group consisting of In 2 O 3 , ZnO, SnO 2 , and Ga 2 O 3. Has been. However, there is no specific description or suggestion of an oxide sintered body containing tin oxide as a main component. Patent Documents 2 and 3 propose ITO films containing gallium. This film needs to contain expensive indium oxide as a main component.
  • Patent Document 4 SnO 2 based sintered body obtained by adding the Ga 2 O 3 to SnO 2 is disclosed.
  • Patent Document 5 describes an amorphous SnO 2 transparent conductive film.
  • this film contains expensive In 2 O 3 as an essential component.
  • first antimony oxide Sb 2 O 3
  • a hot press (HP) method is generally used.
  • sintering is performed while pressure is applied, which is advantageous in improving density and strength to some extent.
  • a cold press (CP) method in which a molded body obtained by press-molding the raw material mixed powder is sintered, or a molded body obtained by casting the raw material mixed powder is sintered. There is a casting method to tie.
  • Sb 2 O 3 is generally used at a temperature of about 1000 ° C., such as in the air, in an oxygen atmosphere, in an inert gas, or in a vacuum. In order to melt in atmospheric conditions, it is necessary to heat-treat at a temperature of at least 1000 ° C. Therefore, when the sintered body is fired by the CP method or the casting method, since the sintering temperature is limited, the sintering does not proceed sufficiently and only a brittle sintered body with insufficient sintering can be obtained. There is a problem.
  • JP-A-7-33030 JP-A-4-272612 JP 2000-129432 A Patent No. 3957917 Japanese Patent No. 3806521
  • the following oxide sintered bodies and the like are provided.
  • Ga 4 containing SnO 8, Ga 4 Sn 5 O 16 and Ga 3 Sn 4 O 12 and one or more stannate gallium compound phase selected from a tin oxide phase An oxide sintered body in which at least one element selected from zinc, aluminum, silicon, indium, germanium, titanium, niobium, tantalum, tungsten, molybdenum, and antimony is dispersed.
  • 2. The oxide sintered body according to 1, wherein the ratio [Ga / (Ga + Sn)] of the gallium element to the total of the gallium element and tin element is 0.01 to 0.80 in atomic ratio. 3. 3. 3.
  • the sintering temperature is set at a heating rate of 0.5 ° C./min or more.
  • an oxide sintered body that does not contain an In element or does not contain a main component, has a low bulk resistance, becomes noduleless during sputtering, can suppress abnormal discharge, An oxide sintered body that is less prone to cracking can be provided. Further, a tin oxide film having a high light transmittance and a method for producing the same can be provided.
  • FIG. 2 is an X-ray diffraction chart of an oxide sintered body produced in Example 1.
  • FIG. 3 is an X-ray diffraction chart of an oxide sintered body produced in Example 2.
  • FIG. 4 is an X-ray diffraction chart of an oxide sintered body produced in Example 3.
  • FIG. 6 is an X-ray diffraction chart of an oxide sintered body produced in Example 4.
  • 6 is an X-ray diffraction chart of an oxide sintered body produced in Example 5.
  • FIG. 6 is an X-ray diffraction chart of an oxide sintered body produced in Example 6.
  • FIG. 7 is an X-ray diffraction chart of an oxide sintered body produced in Example 7.
  • FIG. 10 is an X-ray diffraction chart of an oxide sintered body produced in Comparative Example 6.
  • 10 is an X-ray diffraction chart of an oxide sintered body produced in Comparative Example 7.
  • the oxide sintered body of the present invention contains one or more gallium stannate compound phases selected from Ga 4 SnO 8 , Ga 4 Sn 5 O 16 and Ga 3 Sn 4 O 12 and a tin oxide phase. .
  • at least one element selected from zinc, aluminum, silicon, indium, germanium, titanium, niobium, tantalum, tungsten, molybdenum, and antimony is dispersed. It contains one or two or more gallium stannate compound phases selected from Ga 4 SnO 8 , Ga 4 Sn 5 O 16 and Ga 3 Sn 4 O 12 .
  • the presence of the gallium stannate compound phase in the oxide sintered body enables stable sputtering.
  • gallium stannate compound phases described above in particular, having a Ga 4 SnO 8 phase increases the dispersibility of gallium and suppresses abnormal discharge, thereby enabling stable sputtering. Moreover, since Ga 4 SnO 8 is doped with Sn element, the resistance of the Ga 4 SnO 8 phase is lowered, so that the bulk resistance of the sintered body is reduced. Moreover, there exists an effect which raises sinterability by containing Ga element. Specifically, a Ga 4 SnO 8 phase is precipitated in the sintered body during sintering, and the density of the sintered body increases.
  • the oxide sintered body of the present invention contains a tin oxide phase. By adding the above element such as zinc to the tin oxide phase, the strength of the sintered body can be increased or the bulk resistance can be reduced.
  • the presence of a gallium stannate compound phase and a tin oxide phase in the sintered body can be determined by X-ray diffraction.
  • the measured diffraction spectrum is confirmed by having a JCPDS (Joint Committee on Powder Diffraction Standards) peak pattern of the hexagonal layered compound phase and indium oxide phase, or a similar (shifted) pattern thereof.
  • the ratio [Ga / (Ga + Sn)] of the gallium element to the total of the gallium element and tin element is preferably 0.01 to 0.80 in atomic ratio.
  • a Ga 4 SnO 8 phase can be obtained without the Ga 2 O 3 phase being precipitated during the production of the oxide sintered body (during sintering).
  • the bulk resistance of a sintered compact becomes low, and when it uses as a sputtering target, stable sputtering can be performed.
  • the specific resistance of the manufactured thin film is 0.1 to 100 ⁇ cm depending on the conditions for manufacturing the thin film, which is suitable for semiconductor applications.
  • the ratio of the gallium element is more preferably 0.05 to 0.70, and particularly preferably 0.20 to 0.60. Note that the content (atomic ratio) in the oxide sintered body can be obtained by measuring the abundance of each element by ICP (Inductively Coupled Plasma) measurement.
  • Ga / (Ga + Sn) is preferably 0.25 to 0.80, and particularly preferably 0.3 to 0.50.
  • Ga / (Ga + Sn) is preferably in the range of 0.01 to 0.25. Within this range, the specific resistance of the thin film is 0.0001 to 0.1 ⁇ cm depending on the conditions for producing the thin film, which is suitable for a transparent electrode or the like.
  • Ga / (Ga + Sn) of 0.05 to 0.25 is more preferable because the transparency is improved.
  • Ga / (Ga + Sn) is preferably 0.10 to 0.20.
  • the oxide sintered body of the present invention contains at least one element selected from zinc, aluminum, silicon, indium, germanium, titanium, niobium, tantalum, tungsten, molybdenum and antimony in a dispersed state.
  • the above element is substituted in the tin oxide phase of the oxide sintered body.
  • the above-mentioned elements are dispersed in the oxide sintered body can be confirmed by surface analysis using an electron beam microanalyzer (EPMA).
  • EPMA electron beam microanalyzer
  • the elements need not be aggregated at one place but should be distributed in a plurality of regions. It is preferable that the above elements are uniformly dispersed in the tin oxide phase of the oxide sintered body.
  • each element of zinc, silicon, aluminum, indium, germanium, and titanium is derived from a sintering aid (such as oxide powder of these elements) used during the production of the sintered body.
  • a sintering aid such as oxide powder of these elements
  • the density of the sintered body can be improved.
  • the sintering aid has an effect of promoting the sintering reaction by promoting the firing reaction or generating a liquid phase.
  • a compound of zinc, silicon, indium or aluminum is preferable, and zinc or indium is particularly preferable.
  • each element of niobium, tantalum, tungsten, molybdenum, or antimony is dispersed in the oxide sintered body of the present invention, or by solid solution substitution with Sn in the gallium stannate compound phase and / or tin oxide phase.
  • Niobium, tantalum or antimony is particularly preferable.
  • each element of zinc and indium has an effect of reducing the resistivity of a thin film manufactured when an oxide sintered body is used as a sputtering target.
  • the content of the additive element is preferably 0.08 or less in terms of an atomic ratio with respect to the total amount of all metal elements in the sintered body. If it exceeds 0.08, the bulk resistance of the sintered body may increase, or the thin film produced using the sintered body may be colored.
  • the content of the additive element is more preferably 0.01 to 0.08, and particularly preferably 0.02 to 0.05.
  • the average particle diameter of the tin oxide phase or the gallium stannate compound phase is preferably 5 ⁇ m or less. If the average particle size is 5 ⁇ m or less, abnormal discharge such as arc discharge does not occur during sputtering, and generation of black protrusions called nodules on the target can be suppressed. As a result, a film free from massive foreign matters is obtained on the thin film to be formed. If there are massive foreign substances in the thin film, etching may not be performed properly or a desired pattern may not be formed. Moreover, the upper and lower wiring metals may be short-circuited by foreign substances.
  • an average particle diameter is the value measured by the surface analysis of the electron beam microanalyzer (EPMA). Specifically, the surface analysis of oxygen and metal in a 50 ⁇ 50 micron visual field was performed, the major axis of each phase grain was calculated, and the average value of the particle diameters in the visual field was taken as the average grain size.
  • EPMA electron beam microanalyzer
  • the relative density [(actual density) / (theoretical density)] of the sintered body of the present invention is preferably 85% or more, and more preferably 90% or more.
  • a relative density of 85% or more is preferred because the bulk resistance of the obtained sputtering target does not become too high, and abnormal discharge such as arc discharge does not occur during sputtering.
  • the relative density is 90% or more, it is preferable because cracks and cracks are hardly generated in the sintered body, and a large-sized sintered body can be produced.
  • the relative density can be increased by increasing the Ga concentration.
  • the bulk resistance of the sintered body of the present invention is preferably less than 100 k ⁇ cm. More preferably, it is 5 k ⁇ cm or less, and further preferably 1 k ⁇ cm or less.
  • the sintered body of the present invention is preferably amorphous. Amorphous materials are preferred because they have high scratch resistance and no fine irregularities on the surface of the sintered body.
  • the sintered body of the present invention is obtained by the production method of the present invention described below.
  • the method for producing an oxide sintered body of the present invention includes the following steps (A) to (C).
  • the gallium compound and tin compound powder may be oxides or oxides (oxide precursors) that become oxides after firing.
  • oxide precursors oxides
  • examples of the gallium oxide precursor and tin oxide precursor include gallium or tin sulfide, sulfate, nitrate, halide (chloride, bromide, etc.), carbonate, organic acid salt (acetate, propionate). , Naphthenate, etc.), alkoxide (methoxide, ethoxide, etc.), organometallic complex (acetylacetonate, etc.) and the like.
  • nitrates, organic acid salts, alkoxides, or organometallic complexes are preferred in order to completely thermally decompose at low temperatures so that no impurities remain. It is optimal to use an oxide of each metal.
  • a compound (oxide) containing at least one element selected from zinc, aluminum, silicon, indium, germanium, titanium, niobium, tantalum, tungsten, molybdenum and antimony Etc.) may be added. These compounds function as, for example, a sintering aid.
  • the purity of each raw material is usually 99.9% by mass (3N) or more, preferably 99.99% by mass (4N) or more, more preferably 99.995% by mass or more, particularly preferably 99.999% by mass (5N ) That's it. If the purity of each raw material is 99.9% by mass (3N) or more, the semiconductor characteristics are not deteriorated by impurities such as Fe, Ni, Cu, and the reliability can be sufficiently maintained. In particular, it is preferable that the content of Na, K, and Ca is less than 100 ppm because reliability is improved when a thin film transistor is manufactured.
  • the mixing is preferably carried out by (i) solution method (coprecipitation method) or (ii) physical mixing method. More preferably, a physical mixing method is used for cost reduction.
  • the raw material powder containing the gallium compound and the tin compound is put into a mixer such as a ball mill, a jet mill, a pearl mill, or a bead mill and mixed uniformly.
  • the mixing time is preferably 1 to 200 hours. If it is less than 1 hour, the elements to be dispersed may be insufficiently homogenized, and if it exceeds 200 hours, it may take too much time and productivity may be deteriorated.
  • a particularly preferred mixing time is 10 to 60 hours.
  • the obtained raw material mixed powder preferably has an average particle size of 0.01 to 1.0 ⁇ m.
  • the particle diameter is less than 0.01 ⁇ m, the powder is likely to aggregate, handling is poor, and a dense sintered body may not be obtained. On the other hand, if it exceeds 1.0 ⁇ m, a dense sintered body may not be obtained.
  • the process of calcining the obtained mixture after mixing raw material powder, you may include the process of calcining the obtained mixture.
  • the mixture obtained in the above step is calcined.
  • a heat treatment condition of 200 ° C. or higher and 1 hour or longer is preferable because the raw material compound is sufficiently thermally decomposed. If the heat treatment conditions are 1000 ° C. or less and 100 hours or less, the particles are not coarsened, which is preferable.
  • molding process and sintering process which follow is suitably pulverized using a ball mill, roll mill, pearl mill, jet mill or the like.
  • the average particle size of the mixture after calcining obtained after pulverization is, for example, 0.01 to 3.0 ⁇ m, preferably 0.1 to 2.0 ⁇ m. If the average particle size of the obtained mixture after calcining is 0.01 ⁇ m or more, it is preferable because a sufficient bulk specific gravity can be maintained and handling becomes easy.
  • the average particle diameter of the mixture after calcining is 3.0 ⁇ m or less, it becomes easy to increase the density of the finally obtained sputtering target.
  • the average particle diameter of the mixture after calcining can be measured by the method and method described in JIS R 1619.
  • the molding process is a process in which a mixture of raw material powders (a mixture after calcining when the calcining process is provided) is pressure-molded to form a compact. By this step, the mixture (or the mixture after calcining) is formed into a shape suitable as a sputtering target.
  • Examples of the molding process that can be used in this step include press molding, cold isostatic pressing, uniaxial pressing, mold molding, cast molding, and injection molding.
  • CIP cold isostatic pressure
  • molding aids such as polyvinyl alcohol, methylcellulose, polywax, and oleic acid may be used.
  • the press molding a known molding method such as a cold press method or a hot press method can be used.
  • the obtained mixed powder is filled in a mold and pressure-molded with a cold press machine.
  • the pressure molding is performed at a pressure of 100 to 100,000 kg / cm 2 , preferably 500 to 10,000 kg / cm 2 at normal temperature (25 ° C.), for example.
  • the mixed powder is filled in a mold and a molded body is produced and sintered.
  • the mixed powder is directly sintered in a mold.
  • a dry-type cold press method the raw material after the pulverization step is dried with a spray dryer or the like and then molded.
  • a wet cold press method for example, a filtration molding method (see JP-A-11-286002) is preferably used.
  • This filtration molding method is a filtration molding die made of a water-insoluble material for obtaining a molded body by draining water from a ceramic raw material slurry under reduced pressure, and a lower molding die having one or more drain holes And a water-permeable filter placed on the molding lower mold, and a molding mold clamped from the upper surface side through a sealing material for sealing the filter.
  • the formwork, the sealing material, and the filter are each assembled so that they can be disassembled.
  • a slurry composed of mixed powder, ion-exchanged water and an organic additive is prepared, and this slurry is poured into the filtration mold, Water from the slurry is drained under reduced pressure only from the filter surface side to produce a compact, and the resulting ceramic compact is dried and degreased and then sintered.
  • the sintering temperature may be equal to or higher than the temperature at which the gallium compound reacts with the tin compound to produce a gallium stannate compound phase and a tin oxide phase, preferably 1200 to 1550 ° C., more preferably 1250 to 1500 ° C. 1500 ° C. is particularly preferred. If the sintering temperature is less than 1200 ° C., there is a possibility that gallium oxide-tin oxide based oxides such as Ga 4 SnO 8 , Ga 4 Sn 5 O 16 and Ga 3 Sn 4 O 12 may not be formed. If it exceeds 1550 ° C., the produced compound may be decomposed.
  • the sintering time depends on the sintering temperature, it is preferably 1 to 50 hours, particularly 2 to 30 hours.
  • 0.5 to 10 ° C./min is preferable, 1 to 8 ° C./min is more preferable, and 1 to 5 ° C./min is particularly preferable.
  • the temperature rising temperature is 10 ° C./min or less, sintering is not completed before diffusion, and solid solution substitution is expected to proceed. If it is 0.5 degreeC / min or more, the reaction of a gallium compound and a tin compound will accelerate
  • the sintered body When the rate of temperature rise exceeds 10.0 ° C./min, the sintered body may be broken during the sintering process, or abnormally grown particles may be deposited, and when the sintered body is used as a sputtering target. Uniform film formation may not be possible.
  • Sintering may be performed in an oxidizing atmosphere.
  • the oxidizing atmosphere include an atmosphere in which air or oxygen gas is introduced.
  • it can also sinter under oxygen pressurization.
  • it is preferable to carry out under oxygen inflow and oxygen pressurization.
  • a reduction step may be provided as necessary after the sintering step (C).
  • the bulk resistance of the sintered body obtained in the sintering process can be made uniform as a whole by the reduction process.
  • the reduction method include a method of circulating a reducing gas, a method of sintering in a vacuum, and a method of sintering in an inert gas.
  • reducing gas for example, hydrogen, methane, carbon monoxide, a mixed gas of these gases and oxygen, or the like can be used.
  • inert gas nitrogen, argon, a mixed gas of these gases and oxygen, or the like can be used.
  • the temperature during the reduction treatment is usually 100 to 800 ° C, preferably 200 to 800 ° C.
  • the reduction treatment time is usually 0.01 to 10 hours, preferably 0.05 to 5 hours.
  • the pressure of the reducing gas or inert gas is, for example, 9800 to 1000000 Pa, preferably 98000 to 500000 Pa.
  • the vacuum specifically means a vacuum of about 10 ⁇ 1 to 10 ⁇ 8 Pa, preferably about 10 ⁇ 2 to 10 ⁇ 5 a, and the residual gas is argon, nitrogen or the like. is there.
  • the oxide sintered body obtained by the above production method can be suitably used as a sputtering target.
  • a sputtering target generation of arcing and nodules during film formation can be suppressed, and a crystalline oxide semiconductor film having excellent surface smoothness can be manufactured.
  • the sputtering target can be manufactured by cutting the sintered body into a shape suitable for mounting on a sputtering apparatus as necessary and attaching a mounting jig such as a backing plate.
  • the thickness of the sputtering target is usually 2 to 20 mm, preferably 3 to 12 mm, particularly preferably 4 to 6 mm.
  • the surface of the sputtering target is preferably finished with a 200 to 10,000 diamond grindstone, and particularly preferably finished with a 400 to 5,000 diamond grindstone. It is preferable to use a No. 200-10,000 diamond grindstone because the sputtering target will not break.
  • a plurality of sputtering targets may be attached to one backing plate to substantially form one target. Examples of the backing plate include those made of oxygen-free copper.
  • an oxide semiconductor thin film or an oxide conductive thin film can be obtained by forming a film by a sputtering method or an ion plating method using the target made of the sintered body of the present invention described above.
  • These films are amorphous and have transparency.
  • the light transmittance can be, for example, 82% or more. More preferably, a film of 84% or more, particularly preferably 85% or more is obtained.
  • an oxide semiconductor film formed by a sputtering method is preferable.
  • an RF magnetron sputtering method As a sputtering method, an RF magnetron sputtering method, a DC magnetron sputtering method, an AC magnetron sputtering method, a pulsed DC magnetron sputtering method, or the like is preferably used.
  • the oxygen partial pressure during film formation is preferably 1 vol% or more and less than 20% vol. If it is less than 1% vol, the film immediately after film formation may have conductivity, and use as an oxide semiconductor may be difficult. On the other hand, if it is 20 vol% or more, the film may become an insulator and it may be difficult to use it as an oxide semiconductor. Preferably, it is 3 to 10 vol%.
  • the substrate temperature during film formation is preferably from room temperature to 300 ° C. If it is set below the room temperature or above 300 ° C., the cooling / heating is too expensive. Preferably, the temperature is from room temperature (no substrate heating) to 200 ° C. In the case of continuous sputtering, the substrate may be heated by the plasma being sputtered, and in the case of a film substrate or the like, it is preferable to carry out cooling while keeping the temperature at about room temperature. In the case where a film is formed over a heat-resistant substrate such as a glass substrate, the oxide semiconductor film can be stably and uniformly manufactured by heating the substrate to 150 ° C. to 350 ° C. after sputtering.
  • the stabilization effect is small by heating, and if it exceeds 350 degreeC, heating may be too expensive. 200 ° C to 300 ° C is preferred.
  • the heating time is preferably 10 minutes to 120 minutes. In 10 minutes, the heating effect may not be seen, and in more than 120 minutes, the heating time may be too long and too expensive. 30 minutes to 90 minutes is preferred.
  • the heating atmosphere is preferably an air atmosphere or an oxygen circulation atmosphere.
  • an oxide semiconductor thin film it is considered that electron carriers present in the semiconductor thin film are generated by oxygen vacancies, and the concentration of electron carriers is proportional to the concentration of oxygen vacancies. Therefore, when the electron carrier concentration is controlled, it is necessary to control the oxygen deficiency concentration.
  • the oxygen deficiency concentration can be reduced at a lower heating temperature, which is economical.
  • oxygen vacancies may disappear completely and become an insulator.
  • a preferable oxygen concentration is 5% to 50%, and particularly preferably 10% to 30%.
  • the preferable oxygen concentration is 0 to 50%, preferably 0.1 to 30%, more preferably 0.5 to 20%.
  • the measuring method of the sample obtained in the Example is as follows.
  • (3) Specific Resistance and Light Transmittance of Thin Film The specific resistance was measured with a Mitsubishi Chemical Loresta. The light transmittance was measured as 400 nm to 800 nm for a 100 nm thin film prepared on a glass substrate with a visible spectrophotometer (Shimadzu UV3100), and the average transmittance was determined.
  • Example 1 Production of oxide sintered body 300 g of gallium oxide, 300 g of tin oxide and 5 g of zinc oxide were dispersed in ion-exchanged water, and pulverized and mixed for 10 hours in a bead mill. Next, the obtained slurry was dried and granulated with a spray dryer. This powder was charged into a 140 mm ⁇ mold and pre-molded at a pressure of 100 kg / cm 2 with a mold press molding machine. Next, it compacted with the pressure of 4 t / cm ⁇ 2 > with the cold isostatic press molding machine. The molded body was heated at a temperature increase rate of 500 ° C. or higher at 1.0 ° C./min. And sintered at 1400 ° C.
  • the bulk resistance of the sintered body was 0.160 ⁇ cm. Further, the dispersion state of Ga, Sn, and Zn was confirmed by EPMA measurement in a visual field range of 50 microns. As a result, there were a phase in which Ga and Sn were dispersed and a phase in which only Sn was present, and Zn was dispersed in a phase in which only Sn was present, that is, SnO 2 . As a result, the dispersion state of Ga and Sn was substantially uniform, and the average particle diameters of the tin oxide phase and the gallium stannate phase were 3.5 ⁇ m and 4.2 ⁇ m, respectively.
  • the sintered body on which the target was polished was subjected to a three-point bending test, and the strength was measured. Based on the results, a cumulative failure probability with respect to the bending strength by the median rank method and a Weibull plot with a single mode were prepared, and a Weibull coefficient (m value) indicating variation in the failure probability was obtained. As for the Weibull coefficient, an m value of 10.2 was obtained by obtaining a linear regression line. This means that the larger the Weibull coefficient, the more the non-destructive stress does not vary, but the variation is small and it can be confirmed that the material is stable.
  • the average surface roughness of the surface of the thin film was measured with an AFM apparatus (JSPM-4500, manufactured by JEOL Ltd.) over a range of 10 microns ⁇ 10 microns square, it was very flat at 0.2 nm.
  • the light transmittance of the thin film was 88%.
  • the specific resistance in the hole measurement of the thin film was 10 ⁇ cm, and the carrier concentration was 1.6 ⁇ 10 16 / cm 3 .
  • hole measuring apparatus and its measurement conditions were as follows.
  • Example 2 (1) Production of oxide sintered body 300 g of gallium oxide, 300 g of tin oxide, and 5 g of zinc oxide were dispersed in ion-exchanged water and pulverized and mixed in a bead mill for 72 hours in order to improve dispersibility. Next, the obtained slurry was dried and granulated with a spray dryer. This powder was charged into a 140 mm ⁇ mold, and preformed at a pressure of 100 kg / cm 2 by a mold press molding machine. Next, it compacted with the pressure of 4 t / cm ⁇ 2 > with the cold isostatic press molding machine. The molded body was heated at a temperature increase rate of 500 ° C. or higher at 1.0 ° C./min.
  • the bulk resistance of the sintered body was 0.160 ⁇ cm. Also, when the dispersion state of Ga, Sn, and Zn was confirmed by EPMA measurement in a 50 micron visual field range, there were a phase in which Ga and Sn were dispersed and a phase in which only Sn was present, as in Example 1. Zn was dispersed in a phase having only Sn, that is, SnO 2 . As a result, the dispersion state of Ga and Sn was substantially uniform, and the average particle diameters of the tin oxide phase and the gallium stannate phase were 3.8 ⁇ m and 4.3 ⁇ m, respectively. As in Example 1, a three-point bending test was performed on the polished sintered body and the strength was measured. As a result, the Weibull coefficient (m value) was 10.5. There is no variation in the maximum value, and it can be confirmed that the material is stable with little variation.
  • the surface of the thin film was very flat with an AFM apparatus and Ra was 0.2 nm.
  • the light transmittance of the thin film was 88%.
  • the specific resistance in the hole measurement of the thin film was 15 ⁇ cm, and the carrier concentration was 1.5 ⁇ 10 15 / cm 3 .
  • Example 3 100 g of gallium oxide, 400 g of tin oxide, 10 g of niobium oxide, and a temperature increase rate of 500 ° C. or higher is 2.0 ° C./min.
  • the X-ray diffraction result of the obtained sintered body is shown in FIG. In this result, the tin oxide phase was mainly observed, and the peak of the gallium stannate compound was also observed.
  • the bulk resistance of the sintered body was 0.030 ⁇ cm.
  • the dispersion state was substantially uniform.
  • the relative density of the sintered body was 94%.
  • Example 2 Evaluation of thin film A sputtering target was produced in the same manner as in Example 1 except that the sintered body produced in (1) was used, and a thin film was produced.
  • This thin film was a transparent conductive film.
  • the resulting thin film had a light transmittance of 86%.
  • the specific resistance in the hole measurement of the thin film was 1.5 ⁇ 10 ⁇ 3 ⁇ cm, the carrier concentration was 1.2 ⁇ 10 20 cm ⁇ 3 , and a transparent and low resistance thin film was obtained. Further, when the average surface roughness of the surface of the thin film was measured with an AFM apparatus, Ra was as extremely flat as 0.2 nm.
  • Example 4 100 g of gallium oxide, 400 g of tin oxide and 10 g of niobium oxide were weighed and dispersed in ion-exchanged water, and pulverized and mixed in a bead mill for 72 hours in order to improve dispersibility. Next, the obtained slurry was dried and granulated with a spray dryer. This powder was charged into a 140 mm ⁇ mold, and preformed at a pressure of 100 kg / cm 2 by a mold press molding machine. Next, it compacted with the pressure of 4 t / cm ⁇ 2 > with the cold isostatic press molding machine. The molded body was heated at a heating rate of 500 ° C. or higher at 3.0 ° C./min.
  • the X-ray diffraction result of the obtained sintered body is shown in FIG.
  • the tin oxide phase was mainly observed, and the peak of the gallium stannate compound was also observed.
  • the bulk resistance of the sintered body was as low as 0.010 ⁇ cm.
  • the dispersion state was substantially uniform.
  • the relative density of the sintered body was 95%.
  • Example 2 Evaluation of thin film A sputtering target was produced in the same manner as in Example 1 except that the sintered body produced in (1) was used, and a thin film was produced.
  • This thin film was a transparent conductive film.
  • the resulting thin film had a light transmittance of 87%.
  • the specific resistance in the hole measurement of the thin film was 1.3 ⁇ 10 ⁇ 3 ⁇ cm, the carrier concentration was 1.5 ⁇ 10 20 / cm 3 , and a transparent and low-resistance thin film was obtained. Further, when the average surface roughness of the surface of the thin film was measured with an AFM apparatus, Ra was as extremely flat as 0.2 nm.
  • Example 5 100 g of gallium oxide, 400 g of tin oxide, 10 g of niobium oxide and 10 g of aluminum oxide were weighed and dispersed in ion-exchanged water, and pulverized and mixed in a bead mill for 72 hours in order to improve dispersibility. Next, the obtained slurry was dried and granulated with a spray dryer. This powder was charged into a 140 mm ⁇ mold, and preformed at a pressure of 100 kg / cm 2 by a mold press molding machine. Next, it compacted with the pressure of 4 t / cm ⁇ 2 > with the cold isostatic press molding machine. The molded body was heated at a heating rate of 500 ° C. or higher at 2.0 ° C./min.
  • the X-ray diffraction result of the obtained sintered body is shown in FIG. From this result, the tin oxide phase was mainly observed, and the peak of the gallium stannate compound was also observed.
  • the sintered body had a low bulk resistance of 9.7 ⁇ 10 ⁇ 3 ⁇ cm.
  • the dispersion state was substantially uniform. From the EXAFS measurement at the Nb-K end, it was confirmed that Nb was positive pentavalent and was substituted with SnO 2 phase.
  • the relative density of the sintered body was 96%.
  • Weibull coefficient m value
  • Example 2 Evaluation of thin film A sputtering target was produced in the same manner as in Example 1 except that the sintered body produced in (1) was used, and a thin film was produced.
  • This thin film was a transparent conductive film.
  • the resulting thin film had a light transmittance of 87%.
  • the specific resistance of the thin film in hole measurement was 1.25 ⁇ 10 ⁇ 3 ⁇ cm, the carrier concentration was 2.0 ⁇ 10 20 / cm 3 , and a transparent and low-resistance thin film was obtained. Further, when the average surface roughness of the surface of the thin film was measured with an AFM apparatus, Ra was as extremely flat as 0.2 nm.
  • Examples 6 and 7 A sintered body was produced and evaluated in the same manner as in Example 1 except that the mixing ratio of the raw materials was changed as shown in Table 1. The results are shown in Tables 1 and 2. In the sintered bodies obtained in Examples 6 and 7, the peaks of the tin oxide phase and the gallium stannate compound were observed from X-ray diffraction, and the dispersion state of Ga, Sn, and Zn was confirmed by EPMA measurement. As a result, the dispersion state was substantially uniform.
  • Comparative Example 1 475 g of tin oxide and 25 g of gallium oxide were weighed, added with an aqueous polyvinyl alcohol solution, granulated, and mixed for 20 hours using a ball mill.
  • the mixed powder was filled into a press die having a size of 400 mm ⁇ 800 mm and press-molded at a pressure of 500 Kg / cm 2 .
  • the molding density of the molded body at this time was 3.3 to 3.9 g / cm 3 .
  • the sintered body thus obtained was processed to produce a sputtering target having a size of 300 mm ⁇ 600 mm ⁇ 8 mm.
  • the density of this sputtering target was 5.08 g / cm 3 and the relative density was 88%.
  • the bulk resistance was too high to be measured.
  • the Weibull coefficient (m value) was determined in the same manner as in Example 1, it was 9.2. It was a material with low Weibull coefficient, large variation, and insufficient strength.
  • the specific resistance was 8.0 ⁇ 10 ⁇ 2 ⁇ cm and the carrier concentration was 1.0 ⁇ 10 20 / cm 3 .
  • the light transmittance was 80%.
  • Comparative Example 2 A sintered body was obtained in the same manner as in Example 1 except that 475 g of tin oxide and 25 g of niobium oxide were used. The relative density of the sintered body was 88%, and the bulk resistance was 9.8 ⁇ 10 ⁇ 3 ⁇ cm. When a thin film was produced using this sintered body in the same manner as in Example 1, the specific resistance was 4.5 ⁇ 10 ⁇ 1 ⁇ cm. The light transmittance was 76%.
  • Comparative Example 3 A sintered body was obtained in the same manner as in Example 1 except that 475 g of tin oxide and 25 g of antimony oxide were used. In addition, since antimony oxide has a large amount of evaporation when the temperature is high, the temperature rising rate of 500 ° C. or higher is 15 ° C./min. The sintering temperature was 1000 ° C. and sintering was performed for 15 hours. The density of the sintered body was 73% and the bulk resistance was 120 ⁇ cm. When this sintered body was used to produce a thin film in the same manner as in Example 1, the specific resistance was 5.6 ⁇ 10 ⁇ 2 ⁇ cm. The light transmittance was 79%.
  • Example 2 When a thin film was produced in the same manner as in Example 1 using this sintered target, the specific resistance was 5.6 ⁇ 10 4 ⁇ cm and the light transmittance was 88%. Moreover, when the semiconductor element was produced, the semiconductor characteristic was not shown. Moreover, nodule evaluation was performed on the target in the same manner as in Example 1 (3). As a result, arcing was observed, and the target cracked in 1 hour, making it impossible to discharge.
  • the relative density of this sintered body was 77%, and it was found that the sintered density did not increase. This is because the amount of gallium oxide is too small. Further, the bulk resistance was 1800 ⁇ cm, and from the X-ray diffraction results, only the tin oxide phase was observed as the crystal phase.
  • Example 1 (2) Using this sintered target, a thin film was produced in the same manner as in Example 1 (2).
  • the specific resistance was 3.3 ⁇ 10 ⁇ 2 ⁇ cm.
  • the thin film was colored brown and its light transmittance was 65%.
  • nodule evaluation was performed on the target in the same manner as in Example 1 (3). As a result, abnormal discharge was observed during the sputter discharge, and a large amount of nodules and bubble voids were observed on the surface of the target after the nodule test.
  • Comparative Example 6 A sintered body was obtained in the same manner as in Example 1 except that 300 g of tin oxide and 300 g of gallium oxide were used. The X-ray diffraction result of the obtained sintered body is shown in FIG.
  • Example 1 (3) Using the target made of this sintered body, nodule evaluation was performed in the same manner as in Example 1 (3). As a result, stable discharge could not be performed and sputtering could not be performed.
  • Comparative Example 7 A sintered body was obtained in the same manner as in Example 1 except that 400 g of tin oxide and 100 g of gallium oxide were used. The X-ray diffraction result of the obtained sintered body is shown in FIG.
  • Example 1 shows the raw materials and physical properties of the oxide sintered bodies produced in the examples and comparative examples described above, and Table 2 shows the evaluation of the physical properties and film forming properties of the oxide films.
  • the oxide sintered body of the present invention With the oxide sintered body of the present invention, a sputtering target that does not generate nodules or arcing can be produced.
  • the sputtering target of the present invention is suitable as a material for forming an oxide film.
  • it can be used for semiconductor layers of thin film transistors, formation of oxide semiconductors, transparent electrodes, and the like.
  • the entire contents of the documents described in this specification are incorporated herein by reference.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Cette invention concerne un corps fritté à base d’oxyde caractérisé en ce qu’il contient une ou plusieurs phases de composé de stannate de gallium choisies parmi Ga4SnO8, Ga4Sn5O16 et Ga3Sn4O12, et une phase d’oxyde d’étain. Le corps fritté à base d’oxyde se caractérise aussi en ce qu’au moins un élément choisi parmi le zinc, l’aluminium, le silicium, l’indium, le germanium, le titane, le niobium, le tantale, le tungstène, le molybdène et l’antimoine est dispersé dedans.
PCT/JP2009/060430 2008-08-11 2009-06-08 Corps fritté à base d’oxyde de gallium-oxyde d’étain et film d’oxyde WO2010018707A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010524680A JPWO2010018707A1 (ja) 2008-08-11 2009-06-08 酸化ガリウム−酸化スズ系酸化物焼結体及び酸化物膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008207274 2008-08-11
JP2008-207274 2008-08-11

Publications (1)

Publication Number Publication Date
WO2010018707A1 true WO2010018707A1 (fr) 2010-02-18

Family

ID=41668854

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/060430 WO2010018707A1 (fr) 2008-08-11 2009-06-08 Corps fritté à base d’oxyde de gallium-oxyde d’étain et film d’oxyde

Country Status (3)

Country Link
JP (1) JPWO2010018707A1 (fr)
TW (1) TW201006781A (fr)
WO (1) WO2010018707A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012124408A1 (fr) * 2011-03-14 2012-09-20 富士フイルム株式会社 Procédé de production de film mince semi-conducteur oxyde
JP2012211065A (ja) * 2011-03-22 2012-11-01 Idemitsu Kosan Co Ltd スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法
CN102770577A (zh) * 2010-02-24 2012-11-07 出光兴产株式会社 In-Ga-Sn系氧化物烧结体、靶、氧化物半导体膜、及半导体元件
JP2013040394A (ja) * 2011-08-19 2013-02-28 Jx Nippon Mining & Metals Corp スパッタリング用酸化物焼結体ターゲット及びその製造方法並びに前記ターゲットを用いた薄膜の形成方法及び薄膜形成方法
WO2013065337A1 (fr) * 2011-11-04 2013-05-10 株式会社フェローテックセラミックス Cible de pulvérisation et procédé de production de cette dernière
KR20190114751A (ko) * 2018-03-30 2019-10-10 제이엑스금속주식회사 스퍼터링 타깃 부재 및 그 제조 방법
CN112723875A (zh) * 2021-02-03 2021-04-30 郑州大学 一种氧化镓掺杂氧化锡陶瓷靶材及制备方法
CN115572167A (zh) * 2022-10-18 2023-01-06 长沙壹纳光电材料有限公司 一种iwzo靶材及其制备方法与应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI760539B (zh) * 2017-08-01 2022-04-11 日本商出光興產股份有限公司 濺鍍靶材、氧化物半導體薄膜、薄膜電晶體及電子機器
WO2019097959A1 (fr) * 2017-11-15 2019-05-23 三井金属鉱業株式会社 Corps fritté à base d'oxyde et cible de pulvérisation

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222410A (ja) * 1992-02-17 1993-08-31 Dowa Mining Co Ltd 高密度ｉｔｏ焼結体の製造方法
JPH0935535A (ja) * 1995-07-25 1997-02-07 Sumitomo Metal Mining Co Ltd ＺｎＯ−ＳｎＯ２ 系透明導電性膜
JP2000077358A (ja) * 1998-08-27 2000-03-14 Asahi Glass Co Ltd 透明導電膜、スパッタリングターゲットおよび透明導電膜付き基体
JP2003100154A (ja) * 2001-09-26 2003-04-04 Tosoh Corp 透明導電膜およびその製造方法並びにその用途
JP2005076024A (ja) * 2003-08-29 2005-03-24 Uchitsugu Minami エレクトロルミネッセンス素子用希土類添加酸化ガリウム−酸化錫多元系酸化物蛍光体薄膜の製造方法
WO2007058232A1 (fr) * 2005-11-18 2007-05-24 Idemitsu Kosan Co., Ltd. Couche mince de semi-conducteur et procede de fabrication de celle-ci ainsi que transistor a couches minces
JP2007277075A (ja) * 2006-03-15 2007-10-25 Sumitomo Metal Mining Co Ltd 酸化物焼結体、その製造方法、それを用いた透明導電膜の製造方法、及び得られる透明導電膜

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222410A (ja) * 1992-02-17 1993-08-31 Dowa Mining Co Ltd 高密度ｉｔｏ焼結体の製造方法
JPH0935535A (ja) * 1995-07-25 1997-02-07 Sumitomo Metal Mining Co Ltd ＺｎＯ−ＳｎＯ２ 系透明導電性膜
JP2000077358A (ja) * 1998-08-27 2000-03-14 Asahi Glass Co Ltd 透明導電膜、スパッタリングターゲットおよび透明導電膜付き基体
JP2003100154A (ja) * 2001-09-26 2003-04-04 Tosoh Corp 透明導電膜およびその製造方法並びにその用途
JP2005076024A (ja) * 2003-08-29 2005-03-24 Uchitsugu Minami エレクトロルミネッセンス素子用希土類添加酸化ガリウム−酸化錫多元系酸化物蛍光体薄膜の製造方法
WO2007058232A1 (fr) * 2005-11-18 2007-05-24 Idemitsu Kosan Co., Ltd. Couche mince de semi-conducteur et procede de fabrication de celle-ci ainsi que transistor a couches minces
JP2007277075A (ja) * 2006-03-15 2007-10-25 Sumitomo Metal Mining Co Ltd 酸化物焼結体、その製造方法、それを用いた透明導電膜の製造方法、及び得られる透明導電膜

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
EDWARDS D D: "Subsolidus Phase Relations in the Ga203-In203-Sn02 System.", J. AM. CERAM. SOC., vol. 81, no. 12, December 1988 (1988-12-01), pages 3285 - 3292 *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8999208B2 (en) 2010-02-24 2015-04-07 Idemitsu Kosan Co., Ltd. In-Ga-Sn oxide sinter, target, oxide semiconductor film, and semiconductor element
CN102770577A (zh) * 2010-02-24 2012-11-07 出光兴产株式会社 In-Ga-Sn系氧化物烧结体、靶、氧化物半导体膜、及半导体元件
CN105924137B (zh) * 2010-02-24 2020-02-18 出光兴产株式会社 In-Ga-Sn系氧化物烧结体、靶、氧化物半导体膜、及半导体元件
CN105924137A (zh) * 2010-02-24 2016-09-07 出光兴产株式会社 In-Ga-Sn系氧化物烧结体、靶、氧化物半导体膜、及半导体元件
JP2012191132A (ja) * 2011-03-14 2012-10-04 Fujifilm Corp 酸化物半導体薄膜の製造方法、電界効果型トランジスタ、表示装置及びセンサ
WO2012124408A1 (fr) * 2011-03-14 2012-09-20 富士フイルム株式会社 Procédé de production de film mince semi-conducteur oxyde
JP2012211065A (ja) * 2011-03-22 2012-11-01 Idemitsu Kosan Co Ltd スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法
JP2013040394A (ja) * 2011-08-19 2013-02-28 Jx Nippon Mining & Metals Corp スパッタリング用酸化物焼結体ターゲット及びその製造方法並びに前記ターゲットを用いた薄膜の形成方法及び薄膜形成方法
WO2013065337A1 (fr) * 2011-11-04 2013-05-10 株式会社フェローテックセラミックス Cible de pulvérisation et procédé de production de cette dernière
CN103917688A (zh) * 2011-11-04 2014-07-09 飞罗得陶瓷股份有限公司 溅射靶材及其制造方法
JPWO2013065337A1 (ja) * 2011-11-04 2015-04-02 株式会社フェローテックセラミックス スパッタリングターゲットおよびその製造方法
CN103917688B (zh) * 2011-11-04 2016-06-29 飞罗得陶瓷股份有限公司 溅射靶材及其制造方法
US10504706B2 (en) 2011-11-04 2019-12-10 Ferrotec Ceramics Corporation Sputtering target and method for producing the same
KR102197875B1 (ko) * 2018-03-30 2021-01-04 제이엑스금속주식회사 스퍼터링 타깃 부재 및 그 제조 방법
KR20200140777A (ko) 2018-03-30 2020-12-16 제이엑스금속주식회사 스퍼터링 타깃 부재 및 그 제조 방법
KR20190114751A (ko) * 2018-03-30 2019-10-10 제이엑스금속주식회사 스퍼터링 타깃 부재 및 그 제조 방법
KR20210082410A (ko) 2018-03-30 2021-07-05 제이엑스금속주식회사 스퍼터링 타깃 부재 및 그 제조 방법
CN114574824A (zh) * 2018-03-30 2022-06-03 Ｊｘ金属株式会社 溅射靶部件及其制造方法
CN114592175A (zh) * 2018-03-30 2022-06-07 Ｊｘ金属株式会社 溅射靶部件及其制造方法
CN112723875A (zh) * 2021-02-03 2021-04-30 郑州大学 一种氧化镓掺杂氧化锡陶瓷靶材及制备方法
CN112723875B (zh) * 2021-02-03 2023-01-20 郑州大学 一种氧化镓掺杂氧化锡陶瓷靶材及制备方法
CN115572167A (zh) * 2022-10-18 2023-01-06 长沙壹纳光电材料有限公司 一种iwzo靶材及其制备方法与应用

Also Published As

Publication number Publication date
TW201006781A (en) 2010-02-16
JPWO2010018707A1 (ja) 2012-01-26

Similar Documents

Publication Publication Date Title
WO2010018707A1 (fr) Corps fritté à base d’oxyde de gallium-oxyde d’étain et film d’oxyde
US9202603B2 (en) Sputtering target, transparent conductive film and transparent electrode
US8920683B2 (en) Sputtering target, transparent conductive film and transparent electrode
JP4933756B2 (ja) スパッタリングターゲット
TWI519502B (zh) Ｚｎ－Ｓｎ－Ｏ系氧化物燒結體及其製造方法
US8637124B2 (en) Oxide material and sputtering target
TWI542566B (zh) Ｚｎ－Ｓｉ－Ｏ系氧化物燒結體及其製造方法及透明導電膜
EP2301904B1 (fr) Oxyde complexe fritté, procédé de fabrication d'un oxyde complexe fritté, cible de pulvérisation cathodique et procédé de fabrication d'un film mince
WO2011016388A1 (fr) Fritte d'oxyde, son procédé de production, film conducteur cible et transparent
JP4947942B2 (ja) スパッタリングターゲット
WO2012105323A1 (fr) Corps fritté d'oxyde et comprimés obtenus par traitement de celui-ci
JP2010070418A (ja) ＳｎＯ２−Ｉｎ２Ｏ３系酸化物焼結体及び非晶質透明導電膜
WO2014021374A1 (fr) Corps fritté d'oxyde et comprimé obtenu par le traitement dudit corps
JP2012148937A (ja) 導電性複合酸化物、酸化亜鉛系焼結体、その製造方法およびターゲット
JP5761253B2 (ja) Ｚｎ−Ｓｉ−Ｏ系酸化物焼結体とその製造方法およびスパッタリングターゲットと蒸着用タブレット
JP2012126619A (ja) 酸化亜鉛焼結体およびその製造方法
TW201522689A (zh) 濺鍍靶及其製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09806603

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010524680

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09806603

Country of ref document: EP

Kind code of ref document: A1